Low molecular weight brominated polymers and their use in thermoplastic formulations

ABSTRACT

This invention relates flame retardant compositions containing low molecular weight brominated anionic, chain transfer, vinyl aromatic polymers, hereinafter “ACTVAP”. The compositions can accommodate high bromine content while still exhibiting a low thermally labile bromine content. The compositions have glass transition temperatures, Tg, that are predictive of acceptable melt flows and heat distortion temperatures (HDT) in HIPS and ABS based formulations substrates. The compositions, are suitable flame retardant candidates for use in thermoplastic formulations, e.g. polystyrene and ABS formulations.

TECHNICAL FIELD

This invention relates to flame retardant compositions containingbrominated anionic, chain transfer, vinyl aromatic polymers, hereinafterbrominated “ACTVAP”. The compositions can accommodate high brominecontent while still exhibiting a low thermally labile bromine content.The compositions have glass transition temperatures, T_(g) that arepredictive of acceptable melt flows in high impact polystyrene (HIPS)and acrylonitrile-butadiene-styrene (ABS) based formulations. Articlesproduced from such formulations have good heat distortion temperatures.The compositions, are suitable flame retardant candidates for use inthermoplastic formulations, e.g. HIPS and ABS formulations.

BACKGROUND

Brominated polystyrenic (styrenic polymer) compositions have long beenused as flame retardants in thermoplastic formulations. Brominatedpolystyrenes can be produced by bromination of polystyrenes, thepolystyrenes being derived by free-radical or anionic polymerization ofstyrenic monomer, see for example, commonly-owned U.S. Pat. Nos.5,677,390, 5,686,538, 5,767,203, 5,852,131, 5,852,132, 5,916,978,6,113,381, 6,207,765, 6,232,393, 6,232,408, 6,235,831, 6,235,844,6,326,439, and 6,521,714.

While the forgoing compositions have and are meeting considerablecommercial success, the skilled artisan is always searching for the nextgeneration product that shows commercial promise.

SUMMARY OF THE INVENTION

This invention relates to flame retardant compositions comprising abrominated anionic, chain transfer, vinyl aromatic polymer (ACTVAP),wherein the compositions: (i) contain at least about 72 wt % bromine;and (ii) contain less than about 1,000 ppm (weight/weight) thermallylabile Br, the wt % and ppm values being based upon the total weight ofthe composition. Within the invention scope are compositions in whichthe brominated ACTVAP is brominated anionic, chain transfer styrenepolymer (ACTSP).

ACTVAP and ACTSP, as used herein, are acronyms for, in the first case,vinyl aromatic polymer, and, in the second case, styrene polymer thathave been anionically derived and that have had their respective chainlength distributions determined by a chain transfer mechanism. Thesepolymers are subsequently brominated to yield the flame retardantcompositions of this invention. The chain transfer agent is preferablytoluene.

The use of the chain transfer mechanism allows for the use of catalyticamounts of conventional alkyl lithium polymerization initiators. Thealkyl lithium initiators are also widely used in conventionalpolymerization of styrene. However, there, the polymer growth is notdetermined by chain transfer, but rather, by quenching of the lithiumend-group, thus requiring the use of stoichiometric amounts (rather thancatalytic amounts) of lithium alkyls to obtain the desired polymericchain lengths. Thus, polymers using a chain transfer mechanism todetermine chain length enjoy a considerable cost advantage that inuresto the cost advantage of the compositions of this invention.

The flame retardant compositions of this invention exhibit, amongstother things, a glass transition temperature, i.e. T_(g) that predictsthat the use of such compositions to flame retard HIPS and ABSformulations will not frustrate molding qualities and that moldedarticles produced from such formulations will have acceptable heatdistortion temperatures (HDT).

The combination of a favorable T_(g) combined with a high brominecontent and a low thermally labile bromine content provides aparticularly preferred flame retardant composition of this invention.

The higher bromine content means that the flame retardant compositionsof this invention can deliver more bromine, and hence more flameretardancy, to a HIPS or ABS formulation than the same weight of acomposition having a lower bromine content. That quality offers costsavings opportunities for the manufacturer of the final thermoplasticarticle.

Low thermally labile bromine contents are desired since formulationcompounding and article manufacturing conditions tend to releasethermally labile bromine as HBr, which gas can be destructive ofcompounding and molding equipment.

In regard to bromine in the HIPS or ABS formulation or articles formedtherefrom, it is mentioned that the compositions of this invention areessentially free (less than 50 ppm), if not totally free, of occludedbromine. Occluded bromine is bromine captured in the flame retardantcomposition as Br₂. Significant quantities of such bromine are notdesirable for obvious reasons.

The flame retardant compositions of this invention have athermogravimetric analysis (TGA) profile that predicts that thecompositions are thermally stable enough to not excessively degradeunder compounding and molding conditions but will degrade sufficientlyto release their bromine substituent at the much higher temperaturesexperienced at a “flame front.” The term “flame front” relates to theproximity of a fire to the flame retarded HIPS or ABS article. The firecan be just adjacent the article or emanating from the article itself.

The flame retardant compositions of this invention have good color. Theyare water-white or at least near water-white when tested by the HunterSolution Color Value Test, see the “Analytical Methods” section below.In addition, the compositions have excellent YI values when tested inaccordance with ASTM D1925. Such YI values are associated with thecomposition having a white or near white color when color tested as asolid.

The brominated ACTVAP or ACTSP found in the compositions of thisinvention are derived by the bromination of the corresponding ACTVAP orACTSP. The unbrominated ACTVAP or ACTSP, can also be referred to asprecursor or base ACTVAP or ACTSP. The base ACTVAP or ACTSP can have upto about 25 relative GPC area % monoadduct, e.g. 1,3-diarylpropane. Whenthe aryl groups are phenyl groups, 1,3-diphenylpropane is themonoadduct. However, where desired, the base ACTVAP or ACTSP can bealtered, prior to bromination, to have a lower monoadduct content.Alteration is usually effected by distillation to reduce the monoadductcontent from the base ACTVAP or ACTSP. Such alteration is believed to bedesirable as it is theorized, though this invention is not limited tosuch theory, that the monoadduct tends to brominate quickly and, thus,consume available bromine at a faster rate than that consumed by thehigher molecular weight polymer chains making up the base ACTVAP orACTSP. Such faster bromine consumption is believed to distort the extentand homogeneity of the bromination of the remainder of the highermolecular polymer constituents. Bromination homogeneity concerns thedegree of uniformity in the distribution of aryl bromine along thepolymer chain. The non-end group aryl groups are usually kineticallyslower to brominate and hence harder to highly brominate than theterminal or “end-group” aryl-groups due to steric hindrances resultingfrom the internal molecular structure.

Disproportionate distribution of the bromine between the brominatedmonoadduct and the rest of the polymer constituents in the brominatedACTVAP or ACTSP can result in a flame retardant composition with a lowerglass transition temperature, T_(g), than would otherwise occur. Ifdepressed enough, the lower T_(g) predicts enhanced molding performance(high melt flow index) for the host HIPS or ABS and a reduced heatdistortion temperature (HDT) for articles produced from theflame-retarded HIPS or ABS.

In the following “Detailed Description of the Invention” furtherdescription is given for the compositions of this invention. Thecompositions to which the description applies, in part or in whole, arewithin the scope of the inventions disclosed herein.

Thermoplastic articles containing any one or more of the compositions ofthis invention are within the scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Compositions of this Invention

Compositions of this invention are predominant in brominated ACTVAP orACTSP. Generally, the compositions will contain at least about 97 wt %brominated ACTVAP or ACTSP, with the remainder being by-productimpurities. Such impurities are, for the most part, by-products ofeither the polymerization or bromination processes used to ultimatelyobtain the brominated ACTVAP or ACTSP. Most preferred flame retardantcompositions of this invention contain from about 99 to about 99.95⁺ wt% polymer based on the total weight of the composition.

Base ACTVAP can be represented by the formula:

Ar—CRH[—CH₂CH(Ar)]_(n average)—CH₂CH₂—Ar,

wherein Ar is an aryl group, R is a C₁-C₄ alkyl group and n_(average) isthe average number of repeating units and is based on the number averagemolecular weight, M_(n), of the ACTVAP distribution. n_(average) iscalculated:

n _(average)=(M _(n)−formula wt ArCRH−formula wt ArCH₂CH₂)/(formula wtArCH₂CH₂)

Base ACTSP are those having the structure:

C₆H₅₋CH₂[—CH₂CH(C₆H₅)]n _(average)CH₂CH₂—C₆H₅

wherein the average n_(average) value is determined by the formula:

n _(average)=(M _(n)−196.29)/104.15.

The method of determining the M_(n) for ACTVAP and ACTSP is described inthe “Analytical Methods” section hereof.

The polymerization method for producing base ACTVAP or ACTSP can begenerally described as the anionic polymerization of vinylaromatic/styrene in the presence of toluene solvent (which alsoparticipates as the transfer agent) and a catalytic amount ofbutyllithium that is promoted with N,N,N′,N′-tetramethylethylenediamine(TMEDA). See Examples ACTSP 1-12 herein.

For the reasons discussed previously, the monoadduct content of the baseACTVAP or ACTSP invention is preferred not to exceed about 25 GPC area%. monoadduct, e.g. 1,3-diphenylpropane for ACTSP. (See GPC analysis inthe “Analytical Methods section hereof.) Some base ACTVAP or ACTSP ofthis invention are designed to contain no more than about 10 GPC area %monoadduct, while others are designed to contain no more than about 5GPC area % monoadduct. Almost monoadduct-free base ACTVAP or ACTSP willcontain no more than about 1 GPC area % monoadduct. The compositions ofthis invention will reflect the amount of monoadduct present in the baseACTVAP or ACTSP with their own brominated monoadduct contents of likeGPC area percents. For example, a composition produced from an ACTVAP orACTSP containing less than about 25 GPC area % will in turn contain lessthan about 25 GPC area % brominated monadduct, based on the total weightof the composition.

Since the flame retardant compositions of this invention contain atleast about 97 wt % brominated ACTVAP or ACTSP, and in preferred cases,99 or more wt % brominated ACTVAP or ACTSP, the molecular weightmeasured for the compositions of this invention are considered to be thesame as that for the brominated ACTVAP or ACTSP components. When thecompositions and the brominated ACTVAP or ACTSP of this invention aresubjected to polymeric analysis by GPC (See the “Analytical Methodssection herein), an M_(w) within the range of from about 1,000 to about21,000 Daltons will be measured, preferred is the range of from about1,250 to about 14,000 Daltons. The range for the M_(n) value will bewithin the range of from about 860 to about 18,500 Daltons, preferred isthe range of from about 1070 to about 8,200 Daltons. The polydispersity(M_(w)/M_(n)) is below 2.2 and is generally found to be within the rangeof from about 1.1 and about 1.7.

An important feature of flame retardant compositions of this inventionis their compatibility with the host thermoplastic substrate, e.g. HIPSand ABS formulations. Compatibility is evidenced by the relatively smalldomain size of the compositions of this invention within the articlesformed from the host thermoplastic formulation. Compatibility is afunction of the degree of miscibility of the compositions in the hostthermoplastic substrate. Domain sizes of from about 0.5 to about 2microns are characteristic of compositions of this invention in formedHIPS or ABS articles. Miscibility is considered to be a function ofpolymer size and the composition's T_(g). Generally, non-polymericflame-retardants containing high levels of aryl bromine, e.g. >71 wt %bromine, and high molecular weight brominated polymers do not enjoy thiscompatibility.

Preferred flame retardant compositions of this invention have a T_(g)within the range of from about 35° C. to about 165° C., and preferablywithin the range of from about 75° C. to about 135° C. Such T_(g) valuesportend good moldability when formulated in HIPS or ABS and good HDTvalues for products molded from such formulations. If the T_(g) value istoo high, the molding qualities of the formulation will exhibit too lowof a melt flow, whereas if the T_(g) is too low, HDT values for thefinal molded article can be unacceptably low. The glass transitiontemperature analysis is described in the “Analytical Methods” sectionherein.

The flame retardant compositions of this invention contain at leastabout 65 wt % bromine as determined by analysis of the flame retardantcomposition by X-Ray Fluorescence analysis (See the “Analytical Methods”section herein). Since the brominated ACTVAP or ACTSP components of thecompositions of this invention are produced from very robust and welldesigned base ACTVAP or ACTSP it is possible to apply brominationprocess conditions that will push the bromine content of these polymersto very high levels without attendant excessive thermally labile bromineproduction, and excessive chain degradation. Flame retardantcompositions of this invention contain from about 65 wt % to about 80 wt% bromine. It is believed that a particularly commercially attractiverange will be from about 70 wt % to about 79 wt % bromine. Brominecontents of from about 72 wt % to about 78 wt % bromine are believed tobe most favored from a commercial standpoint. The high bromine contentsfor the flame retardant compositions of this invention should enablelower flame retardant loadings on a weight basis without sacrifice ofthe flame retarding bromine content of the HIPS or ABS end-product. Theforgoing wt % bromine values are based on the total weight of the flameretardant composition.

The flame retardant compositions of this invention, will average fromabout 2 to about 4.8 bromine substituents per aryl group in the polymerdistribution. Preferably, they will average from about 3 to about 4.6bromine substituents per aryl group in the polymer distribution. Thus,each aryl group in the polymer distribution may contain from about 2 toabout 5 bromine substituents per aryl group (on an individual notaverage aryl group basis). The term “polymer distribution” means thetotal polymer constituents as measured by GPC analysis of the flameretardant composition and includes any brominated monoadducts present asa polymer constituent of the distribution. It does not include residualchain transfer agent or styrene monomer if present. As mentionedpreviously, since the compositions of this invention are very high inbrominated ACTVAP or ACTSP, the number of bromine constituents in thecompositions of this invention is essentially the same as for thebrominated ACTVAP or ACTSP. The average number of bromine substituentsis calculated by a combination of wt % bromine via XRF and GPCmeasurement for M_(n). The calculation is illustrated as follows:

For 1 mole of material with the formula,

C₆H_((5-x))Br_(x)CH₂(C₆H_((5-x))B_(x)CHCH₂—)CH₂CH₂-C₆H_((5-x))Br_(x)

where x is the average number of bromine atoms per phenyl group.

then,

x=Br_(moles)/Phenyl_(average)

Total moles of Bromine (Br_(moles)) is given by:

Br_(moles)=(M _(n(unbrominated))·(wt % Br/80)

The average number of phenyl rings in one mole (Phenyl_(average)) isgiven by Phenyl_(average)=2+n_(average)

where:

n _(average)=(M _(n(unbrominated))−196.29)/104.15

and:

M _(n(unbrominated)) =M _(n(brominated))·(1-wt % Br/100),

therefore x is given by

x=Br_(moles)/Phenyl_(average) =M _(n(brominated))·(wt % Br/80)/2+n_(average)

x=M _(n(brominated))·(wt % Br/80)/(2+[(M_(n(unbrominated))−196.29)/104.15])

x=M _(n(brominated))·(wt % Br/80)/(2+[(M _(n(brominated))·(1-wt %Br/100)−196.29)/104.15])

The x values are given for each of the Brominated Examples in Table I.

The wt % bromine is affected by selection of the process parameters forthe bromination of the base ACTVAP or ACTSP. Parameters, such as,bromination time, catalyst used, catalyst amount, reaction solvent,reaction temperature and the amount of bromine present, can influencethe amount of bromination obtained. (See Bromination Examples 1-30)

Despite the relatively high bromine contents of the flame retardantcompositions of this invention, it is a feature of such compositionsthat they exhibit relatively low thermally labile bromine contents.

The amount of thermally labile bromine in the compositions of thisinvention is low and falls within the range of from the detectablelimits of the test to about 1000 ppm (weight/weight and based on thetotal weight of the composition) as measured at 300° C. for 15 minutesin accordance with the method described in the “Analytical Methods”section hereof. Thermally labile bromine contents may also fall withinthe narrower ranges of from the detectable limits of the test to about750 ppm and from the detectable limits of the test to about 500 ppm. SeeBromination Examples 1-30. The detectable limits of the test areevidenced by unacceptable loss of precision, usually occurring whenattempting to measure thermally labile bromine in amounts less than 50ppm. It is to be understood that flame retardant compositions of thisinvention can contain thermally labile bromine amounts lower than about50 ppm when determined by tests that are capable of precision andaccuracy at these low concentrations.

Besides having low thermally labile bromine contents, compositions ofthis invention must be otherwise thermally stable. They must bethermally stable so they do not degrade during the molding orcompounding processes. They also must be stable under expectedconditions of use, transport and storage. But the composition cannot beoverly stable since to function as a flame retardant in the host HIPS orABS substrate, the brominated ACTVAP or ACTSP constituent needs tothermally degrade only in the face of a fire threat. It is a feature ofaryl bromine that, when in admixture with a flame retardant synergist,it does degrade and release its flame retarding bromine at atemperature, which is closely aligned with the temperatures that wouldbe expected at a “flame front.” Such release allows the bromine tointerfere with the flame chemistry and thereby function as a flameretardant.

The flame retardant industry considers Thermal Gravimetric Analysis(TGA) to be an indicator of how a candidate flame retardant will performin actual use. Compositions of this invention have a TGA 5 wt % loss,under nitrogen, at a temperature within the range of from about 290° C.to about 380° C. It is expected that the flame retardant industry willprefer a TGA 5 wt % loss under nitrogen at a temperature within therange of from about 300° C. to about 370° C. Refer to the “AnalyticalMethods” section herein for a description of TGA analysis

Compositions of this invention, as before said have good color. Asmeasured by the Hunter Solution Color Value Test described in the“Analytical Methods” section hereof, the composition obtains Delta Evalues within the range of from about 0.4 to about 17. When the color ismeasured for the solid composition in accordance with ASTM D1925, YIvalues within the range of from about 1 to about 8 are obtained.Preferred YI values are within the range of from about 1 to about 6.

It is within the scope of this invention that the compositions of thisinvention can be used in admixture with other flame retardants, e.g.halogenated non-vinyl aromatic flame retardants, e.g.decabromodiphenylethane, decabromodiphenylether andtetrabromobisphenol-A, provided that such other flame retardants andtheir amounts do not frustrate the obtainment of the desired compositioncharacteristics.

It is to be understood that since most of the compositions of thisinvention are comprised of at least 97 wt % brominated ACTVAP or ACTSP,when quantitative or qualitative values are recited for compositions ofthis invention, such values are considered to also apply to thebrominated ACTVAP or ACTSP itself when applicable, e.g. T_(g), brominewt % content, thermally labile bromine wt % content, TGA, color,molecular weights, etc.

Thermoplastic Formulations of this Invention

The flame retardant compositions of this invention can be used inthermoplastic formulations based on HIPS or ABS. HIPS and ABS are wellknown to the art and are commercially available from several sources.

Preferably the compositions of this invention are used as additive flameretardants and are formulated with the HIPS or ABS based formulation inan amount sufficient to obtain the level of flame retardancy sought,generally a UL 94 rating of V-0 or V-2 for ⅛ inch test strips producedfrom the formulation. The formulation can comprise, and probably willcomprise, other conventional additives. Conventional additives, such asflame retardant synergists, antioxidants, UV stabilizers, dripsuppressants, pigments, impact modifiers, fillers, acid scavengers,blowing agents, and the like, can be included selected and used insuitable amounts in the formulations as is appropriate to achieve thefunction that each additive is to perform. Such selection and amountsare within the routine skill of the artisan. Preferred HIPS and ABSbased formulations of this invention contain a flame retardantsynergist.

Flame retarded HIPS and ABS based formulations contain within the rangeof from about 3 to about 25 wt % flame retardant compositions of thisinvention, the wt % being based on the total weight of the formulation.Preferred amounts are within the range of from about 5 to about 15 wt %.

The flame retardant compositions of this invention are used with flameretarding synergist. These synergists are those that are commonly usedwith aryl brominated flame retardants and are well know in the art.Exemplary of such synergists are iron oxide, zinc borate, or,preferably, antimony oxide synergist, such as, antimony trioxide,antimony pentoxide, potassium antimonite, sodium antimonite. The amountof flame retardant synergist, when used, generally will be in the rangeof up to about 12 wt % based on the total weight of the HIPS or ABSbased formulation. Synergist amounts will most often fall within therange of from about 1 to about 6 wt %. Departures from the foregoingranges of proportions are permissible whenever deemed necessary ordesirable under the particular circumstances at hand, and suchdepartures are within the scope and contemplation of this invention.

This invention includes masterbatch compositions in which flameretardant compositions of this invention are blended with conventionalamounts of common additives and with HIPS or ABS in a weight ratio (HIPSor ABS: composition of the invention) in the range of, say, 1:99 to70:30. Such masterbatch formulations need not, but may also contain atleast one flame retardant synergist such as iron oxide, zinc borate, orpreferably an antimony oxide flame retardant synergist such as antimonytrioxide, antimony pentoxide, potassium antimonite, sodium antimonite.The thus formed masterbatches are suitable to be “let down” in HIPS orABS to form the finished formulation.

Various known procedures can be used to prepare the blends orformulations described herein. For example the HIPS or ABS, the flameretardant composition of this invention and any other components oringredients to be used in the finished formulation can be blendedtogether in powder form and thereafter molded by extrusion, compression,or injection molding. Likewise the components can be mixed together in aBanbury mixer, a Brabender mixer, a roll mill, a kneader, or othersimilar mixing device, and then formed into the desired form orconfiguration such as by extrusion followed by comminution into granulesor pellets, or by other known methods.

Preferred flame retarded HIPS or ABS formulations described herein orthose that have the capability of forming molded specimens of 3.2millimeter thickness (⅛-inch thickness) that pass at least the UL 94 V0test. Less preferred, but still having commercial utility, are thoseHIPS or ABS formulations having the capability of forming moldedspecimens 1.6 millimeter ( 1/16-inch) thick that obtain a UL 94 V2rating.

ANALYTICAL METHODS

Known analytical methods can be used or adapted for use in assaying thecharacteristics of the compositions and formulations of this invention.

Total Bromine Content.

Since the compositions of this invention have good, or at leastsatisfactory, solubility in solvents such as tetrahydrofuran (THF), thedetermination of the total bromine content for the compositions of thisinvention is easily accomplished by using conventional X-RayFluorescence techniques. The sample analyzed is a dilute sample, say 0.1g+/−0.05 g in 60 mL THF. The XRF spectrometer can be a Phillips PW1480Spectrometer. A standardized solution of bromobenzene in THF is used asthe calibration standard. The total bromine values described herein andreported in the Examples are all based on the XRF analytical method.

Hunter Solution Color Value Test.

To determine the color attributes of the flame retardant compositions ofthis invention, use is again made of the ability to dissolve thesecompositions in easy-to-obtain solvents, such as chlorobenzene. Theanalytical method used is quite straight-forward. Weigh 5 g+/−0.1 g ofthe composition into a 50 mL centrifuge tube. To the tube also add 45g+/−0.1 g chlorobenzene. Close the tube and shake for 1 hour on a wristaction shaker. After the 1 hour shaking period, examine the solution forundissolved solids. If a haze is present, centrifuge the solution for 10minutes at 4000 rpm. If the solution is still not clear, centrifuge anadditional 10 minutes. Should the solution remain hazy, then it shouldbe discarded as being incapable of accurate measurement. If, however,and this is the case most of the time, a clear solution is obtained, itis submitted for testing in a HunterLab Color Quest SphereSpectrocolorimeter. A transmission cell having a 20-mm transmissionlength is used. The colorimeter is set to “Delta E-lab” to report coloras AE and to give color values for “L”, “a” and “b”. Product color isdetermined as total color difference (ΔE) using Hunter L, a, and bscales for the 10% by weight concentrations of the product inchlorobenzene versus chlorobenzene.

Yellowness Index Hunter Colorimeter

Compositions of this invention were subjected to the analysis describedin ASTM D1925

T_(g) Values

T_(g) values were obtained by DSC with a TA Instruments DSC Model 2920.Samples were heated to 400° C. at a rate of 10° C./min under nitrogen.T_(g) is determined by noting the change in the specific heat of apolymer at the glass to rubber transition. This is a second orderendothermic transition (requires heat to go through the transition). InDSC, the transition appears as a step transition and not a peak such asmight be seen with a melting transition. See, The Elements of PolymerScience and Engineering, An introductory Text for Engineers and Chemist,Alfred Rudin, Academic Press, Orlando Fla., 1982, pg 403.

Thermogravimetric Analysis.

Thermogravimetric analysis (TGA) is also used to test the thermalbehavior of the flame retardant compositions of this invention. The TGAvalues are obtained by use of a TA Instruments ThermogravimetricAnalyzer. Each sample is heated on a Pt pan from 25° C. to about 600° C.at 10°C./min with a nitrogen flow of 50-60 mL/min.

Thermal Stability Test (Thermally Labile Bromine Test).

This test procedure essentially as described in U.S. Pat. No. 5,637,650.In conducting this test, each sample is run in duplicate. A 2.00g+/−0.01 g sample is placed into a new clean 20 mm by 150 mm test tube.With a neoprene stopper and Viton® fluoroelastomer tubing, the test tubeis connected to a nitrogen purge line with exit gas from the test tubebeing passed successively through subsurface gas dispersion frits inthree 250-mL sidearm filter flasks each containing 200 mL of 0.1 N NaOHand 5 drops of phenolphthalein. With a constant nitrogen purge at 0.5SCFH, the test tube is heated at 300° C. in a molten salt bath (51.3%KNO₃/48.7% NaNO₃) for 15 minutes followed by 5 minutes at ambienttemperature. The test tube containing the sample is then replaced with aclean dry test tube, and the apparatus is purged with nitrogen for anadditional 10 minutes with the empty test tube in the 300° C. salt bath.The test tube, tubing and gas dispersion tubes are all rinsed withdeionized water, and the rinse is combined quantitatively with thesolutions in the three collection flasks. The combined solution isacidified with 1:1 HNO₃ and titrated with 0.01 N AgNO₃ using anautomatic potentiometric titrator (Metrohm 670, 716, 736, orequivalent). Results are calculated as ppm HBr ppm: HBr=(mL AgNO₃ to endpoint)·(normality of AgNO₃) (80912)/(sample wt.). The tubing isthoroughly dried with nitrogen before the next analysis. Each day beforethe first sample, three empty clean test tubes are run as blanks toassure there is no residual hydrogen halide in the system.

GPC Molecular Weights for Brominated ACTVAP/ACTSP

The M_(w), M_(n), M_(z), M_(p) and PD values were obtained by GPC usinga Waters model 510 HPLC pump and, as detectors, a Waters RefractiveIndex Detector, Model 410 and a Precision Detector Light ScatteringDetector, Model PD2000. The columns were Waters, [mu]Styragel, 500 Å,10,000 Å and 100,000 Å. The auto-sampler was a Shimadzu, Model Sil 9A. Apolystyrene standard (M_(w)=185,000) was routinely used to verify theaccuracy of the light scattering data. The solvent used wastetrahydrofuran, HPLC grade. Based on isolated 1,3diphenylpropane and1,3,5-triphenylpentane adducts, and the mode of separation is sizeexclusion, peaks are identified according to their order of elution as1,3-diphenylpropane, 1,3,5-triphenylpentaned,1,3,5,7-tetraphenylheptaned, 1,3,5,7,9-pentaphenylnonane, etc. Theindividual peaks of the oligomeric material are then assignedtheoretical molecular weight values. A calibration curve is constructedusing these theoretical values and their corresponding retention times.Based on this calibration, the overall distribution data is calculatedand reported. The test procedure used entailed dissolving 0.015 g-0.020g of sample in 10 mL of THF. An aliquot of this solution is filtered and50 L is injected on the columns. The separation was analyzed usingsoftware provided by Precision Detectors for the PD 2000 LightScattering Detector.

GPC Molecular Weights for Base ACTVAP and ACTSP

The M_(w), M_(n), M_(p), M_(z) and PD values were obtained by GPC usinga modular system with a Shimadzu autosampler (model SIL-9), a Shimadzurefractive index detector (model RID-6A), a Waters HPLC pump (model 510)and a Waters TCM column heater. The columns were Polymer Labs (Varian)Oligopore columns, 300 mm by 7.5 mm, part number 1113-6520, orequivalent. The solvent used was tetrahydrofuran, HPLC grade. The testprocedure used entailed dissolving 0.10 g of sample in 10 mL of THF. Analiquot of this solution is filtered and 50 μL is injected on thecolumns. The calculations were performed by the Viscotek Omnisec,version 4.2.0.237 (or equivalent) gel permeation chromatography (GPC)data collection and processing system.

Analytical Methods for Molding Articles:

HDT was determined by ASTM D 648; Vicat, ° C. by ASTM D 649; Izod Impactby ASTM D 256; Melt Flow Index by ASTM D 1238; and UL-94, ⅛″ (32 mm)rating by UL 94.

The following Examples illustrate principles of this invention and arenot intended to limit the generic scope of this invention.

EXAMPLES ACTSP Examples 1-10

General: A spherical glass 12 liter creased reactor with oil jacket wasequipped with a reflux condenser, distillation head, submerged thermalcouple, bottom drain valve, and stainless steel internal cooling coils.Temperature was tightly maintained at a set point via PID controllerthat regulates water flow to the cooling coils. Vigorous agitation wasaccomplished by means of a overhead stirring assembly comprised of 19 mmOD glass shaft with two sets of glass impellers, one set pitched and theother flat, fused to the shaft. The reactor was essentially free of allwetted PTFE parts or other polymeric fluorinated materials orelastomers.

In all examples the reactor was maintained under an inert dry N₂atmosphere during all operations. The reactor was charged with the chaintransfer agent(s) through a dip leg by means of a diaphragm pump. Alkyllithium, metal alkoxides (when used), additional solvents and the aminepromoter (TMEDA) were all fed subsurface to the stirred chain transferagent(s) in that order through the same dip leg. Styrene was pumped intothe reactor by means of a metering pump through a 3″ (76.2 mm)cylindrical column (1.75″ (44.45 mm) dia. ≈100 g) of Basic AluminumOxide (EMD Chemicals, Aluminum oxide 90, mesh 70-230, columnchromatography grade) and delivered as a fine stream or spray above thesurface of the reaction mixture through two 1/16″ (16 mm) OD feednozzles.

Example 1 ACTSP-1 M_(w)=483 PD=1.32

Toluene, 4323 g (5.0 liters, 46.92 mol) was charged to the reactorpreviously heated to 70° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 70° C. As the contentof the reactor was heated to the reaction temperature, 63.94 g n-BuLisolution (2M in cyclohexane, 0.165 mol) was charged through the dip legbelow the surface of the gently agitated (300 rpm) toluene reactionmixture. The feed line was then flushed with 75 ml of anhydrous toluene.Next a previously prepared solution comprised of potassium t-butoxide(18.28 g, 0.163 mol), TMEDA (94.26 g, 0.811 mol), and toluene (421.27 g,4.7 mol) was introduced forming a characteristic bright red color of aTMEDA complexed benzyl anion with concomitant off gassing of butane. Thesubsurface line was flushed with a second 75 ml aliquot of anhydroustoluene via metering pump. An additional 350 ml of anhydrous toluene wasfed at a constant rate during the anionic chain transfer polymerizationprocess. Reactor agitation was increased to 510 rpm and 2523 g ofstyrene (99+%, 24.22 mol) were fed over 150 minutes. The well-calibratedmetering pump was programmed to feed at a constant rate of 16.82 g/min.Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed systemto flush the alumina bed and complete the styrene feed. The styrene feedto the reactor was deemed complete when no further heat of reaction wasobserved, generally signified by the automated closing of the solenoidvalve on the reactor's cooling coils.

The reaction mixture was quenched at 70° C. with a 50 ml aliquot ofdeoxygenated water resulting in a water white turbid mixture. Thereaction mixture was washed with deoxygenated water (3×650 ml) phasecuts could be made after some settling time. Water and any rag oremulsion was removed through the bottom drain valve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Residual moisture wasremoved over a period of approximately two hours as the pot temperatureclimbed from 65° C. to 115° C.; while water, cyclohexane and sometoluene were distilled. An analytical sample was removed, GPC analysisprovided the following data: M_(p): 197, M_(n): 331, M_(w): 368, M_(z):406, PD: 1.11.

The crude reaction mixture, 7027 g, was stripped in a continuousoperation of excess toluene to yield 3231 g of the concentrated productstream that had the following GPC analysis: M_(p): 300, M_(n): 367,M_(w): 483, M_(z): 634, PD: 1.32. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions: feed rate=1.33 L/hr, oil jacket temperature=185° C.,Pressure=50 mm Hg and condenser temperature=0° C. An additional 440 g oftoluene was collected in a dry ice trap, while the cold finger condensed3280 g of a mixture of toluene and 1,3-diphenylpropane free ofstructural isomers.

Example 2 ACTSP-2 M_(w)=496 PD=1.32

Toluene, 4763 g (5.5 liters, 51.69 mol) was charged to the reactorpreviously heated to 80° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 80° C. As the solventwas heated to the reaction temperature, 111.65 g n-BuLi solution (2M incyclohexane, 0.288 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 80° C., 49.46 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.426 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2951 g of styrene (99+%, 28.33 mol) were fedover 180 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 16.4 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The PID temperature controller was left at 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(3×650 ml). Phase cuts were rapid and required little settling time.Water and any rag or emulsion was removed through the bottom drainvalve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed. An aliquot wasremoved for analysis via GPC (M_(p): 195, M_(n): 300, M_(w): 416, M_(z):624, PD: 1.38)

The crude reaction mixture, 804 g, was stripped via continuous operationof excess toluene to yield 4011 g of an intermediate product stream thathad the following GPC analysis: M_(r): 191, M_(n): 314, M_(w): 426,M_(z): 615, PD: 1.40. The continuous strip was accomplished by means ofwiped film evaporator (WFE, aka. Pope Still). WFE operating conditionswere as follows: feed rate=1.33 L/hr, oil jacket temperature=190° C.,Pressure=55 mm Hg and condenser temperature=0° C. An additional 918 g oftoluene was collected in a dry ice trap, while the cold finger condensed2942 g of a mixture of toluene and 1,3-diphenylpropane.

A second pass of the 855.4 g of the concentrate through the WFE produced698 g of an oligomeric mixture with the following GPC profile: M_(r):298, M_(n): 375, M_(w): 496, M_(z): 715, PD: 1.32. WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=200° C., Pressure=10 mm Hg and condenser temperature=0° C. Amixture (155 g) of 1,3-Diphenylpropane and traces of its structuralisomers (methylated diphenylethanes) were collected as a distillate.

Example 3 ACTSP-3 M_(w)=530 PD=1.47

Toluene, 4758 g (5.5 liters, 51.64 mol) was charged to the reactorpreviously heated to 90° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 90° C. As the solventwas heated to the reaction temperature, 73.37 g n-BuLi solution (2M incyclohexane, 0.189 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 90° C., 32.72 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.282 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2933 g of styrene (99+%, 28.16 mol) were fedover 150 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 19.5 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The PID temperature controller was set at 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(3 times, 650 ml). Phase cuts were rapid and required little settlingtime. Water and any rag or emulsion was removed through the bottom drainvalve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed. An aliquot wasremoved for analysis via GPC (M_(p): 196, M_(n): 363, M_(w): 555, M_(z):977, PD: 1.53)

The crude reaction mixture, 8062 g, was stripped via continuousoperation of excess toluene to yield 3837 g of the concentrated productstream that had the following GPC analysis: M_(p): 196, M_(n): 359,M_(w): 530, M_(z): 868, PD: 1.47. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=175° C., Pressure=70 mm Hg and condenser temperature=0° C.An additional 1182 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 2896 g of a mixture of toluene and1,3-diphenylpropane.

Example 4 ACTSP-4 M_(w)=584 PD=1.50

Toluene, 5801 g (6.7 liters, 62.95 mol) was charged to the reactorpreviously heated to 115° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 115° C. As thesolvent was heated to near reflux, 78.31 g n-BuLi solution (2M incyclohexane, 0.202 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 110° C., 24.73 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.213 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2543 g of styrene (99+%, 24.42 mol) were fedover 120 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 21.2 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The PID temperature controller was set to 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(3 times, 650 ml). Phase cuts were rapid and required little settlingtime. Water and any rag or emulsion was removed through the bottom drainvalve.

The temperature oil jacket was increased to 130° C. while the controlvalve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed. An aliquot wasremoved for analysis via GPC (M_(r): 185, M_(n): 322, M_(w): 457, M_(z):648, PD: 1.42)

The crude reaction mixture, 8528 g, was stripped via continuousoperation of excess toluene to yield 3253 g of the concentrated productstream that had the following GPC analysis: M_(r): 300, M_(n): 389,M_(w): 584, M_(z): 887, PD: 1.50. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=170° C., Pressure=95 mm Hg and condenser temperature=0° C.An additional 1154 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 4092 g of a mixture of toluene and1,3-diphenylpropane.

Example 5 ACTSP-5 M_(w)=715 PD=1.40

Toluene, 5848 g (6.76 liters, 63.46 mol) was charged to the reactorpreviously heated to 115° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 115° C. As thesolvent was heated to near reflux, 78. g n-BuLi solution (2M incyclohexane, 0.202 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 110° C., 24.0 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.207 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2548 g of styrene (99+%, 24.46 mol) were fedover 110 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 23.2 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The PID temperature controller was set to 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(three times, 650 ml). Phase cuts were rapid and required littlesettling time. Water and any rag or emulsion was removed through thebottom drain valve.

The temperature oil jacket was increased to 130° C. while the controlvalve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed. An aliquot wasremoved for analysis via GPC (M_(r): 194, M_(n): 382, M_(w): 595, M_(z):998, PD: 1.56)

The crude reaction mixture, 8660 g, was stripped via continuousoperation of excess toluene to yield 3217 g of an intermediate productstream that had the following GPC analysis: M_(r): 297, M_(n): 399,M_(w): 613, M_(z): 1003, PD: 1.54. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=165° C., Pressure=90 mm Hg and condenser temperature=0° C.An additional 813 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 4600 g of a mixture of toluene and1,3-diphenylpropane.

A second pass of the concentrate through the WFE produced 2453 g of anoligomeric mixture with the following GPC profile: M_(r): 400, M_(n):512, M_(w): 715, M_(z): 1084, PD: 1.4. WFE operating conditions were asfollows: feed rate=1.33 L/hr, oil jacket temperature=205° C.,Pressure=0.6 mm Hg and condenser temperature=0° C. A mixture (69 g) of1,3-Diphenylpropane and its structural isomers (methylateddiphenylethanes) were collected as a distillate.

Example 6 ACTSP-6 M_(w)=740 PD=1.66

Toluene, 4758 g (5.5 liters, 51.64 mol) was charged to the reactorpreviously heated to 80° C. by means of the hot oil jacket. The PIDcontroller operating the cooling coils was set for 80° C. As the solventwas heated to the reaction temperature, 70.2 g n-BuLi solution (2M incyclohexane, 0.181 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 80° C., 32.99 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.284 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2933 g of styrene (99+%, 28.16 mol) were fedover 180 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 16.3 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The PID temperature controller was left at 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(3 times, 650 ml). Phase cuts were rapid and required little settlingtime. Water and any rag or emulsion was removed through the bottom drainvalve.

The temperature oil jacket was increased to 130° C. while the controlvalve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed.

An aliquot was removed for analysis via GPC (M_(e): 192, M_(n): 425,M_(w): 727, M_(z): 1398, PD: 1.71)

The crude reaction mixture, 7931 g, was stripped via continuousoperation of excess toluene to yield 3490 g of the concentrated productstream that had the following GPC analysis: M_(e): 295, M_(n): 446,M_(w): 740, M_(z): 1357, PD: 1.66. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=185° C., Pressure=70 mm Hg and condenser temperature=0° C.An additional 917 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 3340 g of a mixture of toluene and1,3-diphenylpropane.

Example 7 ACTSP-7 M_(w)=800 PD=1.39

Toluene 4758 g, (5.5 liters, 51.64 mol) was charged to the reactorpreviously heated to reflux and azeotropically dried over a 4 hourperiod; Karl Fisher moisture analysis indicated 15 ppm residual H₂O. Thedried toluene was cooled to 75° C. with the oil jacket and PIDcontroller operating the cooling coils both set at that temperature.Upon cooling to the set point temperature, 109.3 g n-BuLi solution (2Min cyclohexane, 0.282 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Next, 48.7 gof N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.419 mol) was chargedto the reactor through the subsurface feed line forming thecharacteristic bright red color of TMEDA complexed benzyl lithium anionwith concomitant off gassing of butane. The subsurface line was flushedwith a second 75 ml aliquot of anhydrous toluene via metering pump.Additionally 350 ml of anhydrous toluene was fed at a constant rateduring the anionic chain transfer polymerization process. Reactoragitation was increased to 510 rpm and 2940 g of styrene (99+%, 28.23mol) were fed over 180 minutes. The well-calibrated metering pump wasprogrammed to feed at a constant rate of 16.3 g/min. Anhydrouscyclohexane (2×200 ml) was charged to the styrene feed system to flushthe alumina bed. The styrene feed to the reactor was deemed completewhen no further heat of reaction was observed generally signified by theclosing of the automated control valve on the coiling coils.

The set point of PID temperature controller was maintained at 75° C. andwater was fed through the cooling coils as needed while the flow of thehot oil was altered to bypass the reactor jacket. The reaction mixturewas quenched at 75° C. with a 50 ml aliquot of deoxygenated waterresulting in a water white turbid mixture. The reaction mixture waswashed with deoxygenated water (3 times, 650 ml). Phase cuts were rapidand required little settling time. Water and any rag or emulsion wasremoved through the bottom drain valve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillationapparatus. An aliquot was removed for analysis via GPC (M_(p): 192,M_(n): 447, M_(w): 713, M_(z): 1196, PD: 1.59)

The crude reaction mixture, 8068 g, was stripped via continuousoperation of excess toluene to yield 3380 g of an intermediate productstream that had the following GPC analysis: M_(e): 297, M_(n): 476,M_(w): 733, M_(z): 1191, PD: 1.54. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=185° C., Pressure=55 mm Hg and condenser temperature=0° C.Additionally 1935 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 261 g of a mixture of toluene and1,3-diphenylpropane.

A second pass of the concentrate through the WFE produced 2715 g of anoligomeric mixture with the following GPC profile: M_(p): 398, M_(n):577, M_(w): 800, M_(z): 1186, PD: 1.39. WFE operating conditions were asfollows: feed rate=1.33 L/hr, oil jacket temperature=185° C.,Pressure=0.1 mm Hg and condenser temperature=0° C. A mixture (388 g) of1,3-Diphenylpropane and its structural isomers (methylateddiphenylethanes) were collected as a distillate.

Example 8 ACTSP-8 M_(w)=817 PD=1.30

Toluene, 4332 g (5.0 liters, 47.02 mol) was charged to the reactorpreviously heated to 75° C. by means of the hot oil Jacket. The PIDcontroller operating the cooling coils was set for 70° C. As the contentof the reactor was heated to the reaction temperature, 94 g n-BuLisolution (2M in cyclohexane, 0.242 mol) was charged through the dip legbelow the surface of the gently agitated (300 rpm) toluene reactionmixture. The feed line was then flushed with 75 ml of anhydrous toluene.Next a previously prepared solution comprised of potassium t-butoxide(27.32 g, 0.243 mol), TMEDA (35.95 g, 0.309 mol), THF (59.93 g, 0.831mol) and toluene (433.36 g, 4.7 mol) was introduced forming acharacteristic bright red color of a TMEDA complexed benzyl anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2528 g of styrene (99+%, 24.27 mol) were fedover 150 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 16.81 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed andcomplete the styrene feed. The styrene feed to the reactor was deemedcomplete when no further heat of reaction was observed, generallysignified by the automated closing of the solenoid valve on thereactor's cooling coils.

The reaction mixture was quenched at 70° C. with a 50 ml aliquot ofdeoxygenated water resulting in a water white turbid mixture. Thereaction mixture was washed with deoxygenated water (3 times, 650 ml)phase cuts though not easy could be made after some settling time. Waterand any rag or emulsion was removed through the bottom drain valve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Residual moisture wasremoved over a period of approximately two hours as the pot temperatureclimbed from 65 to 115° C.; water, cyclohexane, THF and toluene takenoverhead. An aliquot was removed for analysis via GPC provided thefollowing data: M_(p): 405, M_(n): 509, M_(w): 790, M_(z): 1180, PD:1.55.

The crude reaction mixture, 7215 g, was stripped in a continuousoperation of excess toluene to yield 2894 g of an intermediate productstream that had the following GPC analysis: M_(p): 402, M_(n): 530,M_(w): 767, M_(z): 1039, PD: 1.45. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions: feed rate=1.33 L/hr, oil jacket temperature=185° C.,Pressure=55 mm Hg and condenser temperature=0° C. An additional 1435 gof toluene was collected in a dry ice trap, while the cold fingercondensed 2884 g of a mixture of toluene and 1,3-diphenylpropane.

A second pass of the product stream through the WFE produced 2415 g of aoligomeric mixture with the following GPC profile: M_(p): 409, M_(n):645, M_(w): 817, M_(z): 1009, PD: 1.27. WFE operating conditions: feedrate=1.33 L/hr, oil jacket temperature=185° C., Pressure=0.1 mm Hg andcondenser temperature=0° C. 271 g of 1,3-diphenylpropane free ofstructural isomers was collected as a distillate.

Example 9 ACTSP-9 M_(w)=928 PD=1.43

Toluene 4758 g, (5.5 liters, 51.64 mol) was charged to the reactorpreviously heated to reflux and azeotropically dried over a 4 hourperiod; Karl Fisher moisture analysis indicated 16 ppm residual H₂O. Thedried toluene was cooled to 80° C. with the oil jacket and PIDcontroller operating the cooling coils both set at that temperature.Upon cooling to the set point temperature, 71.00 g n-BuLi solution (2Min cyclohexane, 0.183 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Next, 33.2 gof N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.286 mol) was chargedto the reactor through the subsurface feed line forming thecharacteristic bright red color of TMEDA complexed benzyl lithium anionwith concomitant off gassing of butane. The subsurface line was flushedwith a second 75 ml aliquot of anhydrous toluene via metering pump. Anadditional 350 ml of anhydrous toluene was fed at a constant rate duringthe anionic chain transfer polymerization process. Reactor agitation wasincreased to 510 rpm and 2939 g of styrene (99+%, 28.22 mol) were fedover 180 minutes. The well-calibrated metering pump was programmed tofeed at a constant rate of 16.3 g/min. Anhydrous cyclohexane (2×200 ml)was charged to the styrene feed system to flush the alumina bed. Thestyrene feed to the reactor was deemed complete when no further heat ofreaction was observed generally signified by the closing of theautomated control valve on the cooling coils.

The set point of PID temperature controller was maintained at 80° C. andwater was fed through the cooling coils as needed while the flow of thehot oil was altered to bypass the reactor jacket. The reaction mixturewas quenched at 80° C. with a 50 ml aliquot of deoxygenated waterresulting in a water white turbid mixture. The reaction mixture waswashed with deoxygenated water (3×650 ml). Phase cuts were rapid andrequired little settling time. Water and any rag or emulsion was removedthrough the bottom drain valve.

The temperature of the oil jacket was increased to 130° C. while thecontrol valve to the cooling coils was turned off. Cyclohexane, residualmoisture and toluene were distilled through a simple distillation head(1 atm.) until a pot temperature of 115° C. was observed. An aliquot wasremoved for analysis via GPC (M_(r): 306, M_(n): 505, M_(w): 824, M_(z):1314, PD: 1.63)

The crude reaction mixture, 7589 g, was stripped via continuousoperation of excess toluene to yield 3382 g of an intermediate productstream that had the following GPC analysis: M_(r): 305, M_(n): 539,M_(w): 852, M_(z): 1342, PD: 1.58. The continuous strip was accomplishedby means of wiped film evaporator (WFE, aka. Pope Still). WFE operatingconditions were as follows: feed rate=1.33 L/hr, oil jackettemperature=185° C., Pressure=55 mm Hg and condenser temperature=0° C.An additional 1430 g of toluene was collected in a dry ice trap, whilethe cold finger condensed 2634 g of a mixture of toluene and1,3-diphenylpropane.

A second pass of the concentrate through the WFE produced 3012 g of anoligomeric mixture with the following GPC profile: M_(r): 409, M_(n):648, M_(w): 928, M_(z): 1390, PD: 1.43. WFE operating conditions were asfollows: feed rate=1.33 L/hr, oil jacket temperature=205° C.,Pressure=0.6 mm Hg and condenser temperature=0° C. A mixture (455 g) of1,3-Diphenylpropane and its structural isomers (methylateddiphenylethanes) were collected as a distillate.

Example 10 ACTSP-10 M_(w)=1194 PD=1.77

Toluene, 5798 g (6.7 liters, 62.92 mol) was charged to the reactorpreviously heated to 110° C. by means of the hot oil jacket. The PIDcontroller operating the coiling coils was set for 115° C. As thesolvent was heated to the reaction temperature, 79.6 g n-BuLi solution(2M in cyclohexane, 0.205 mol) was charged through the dip leg below thesurface of the gently agitated (300 rpm) toluene reaction mixture. Thefeed line was then flushed with 75 ml of anhydrous toluene. Once the pottemperature reached 110° C., 24.2 g ofN,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.208 mol) was charged tothe reactor through the subsurface feed line forming the characteristicbright red color of TMEDA complexed benzyl lithium anion withconcomitant off gassing of butane. The subsurface line was flushed witha second 75 ml aliquot of anhydrous toluene via metering pump.Additionally 350 ml of anhydrous toluene was fed at a constant rateduring the anionic chain transfer polymerization process. Reactoragitation was increased to 510 rpm and 2544 g of styrene (99+%, 24.43mol) were fed over 80 minutes. The well-calibrated metering pump wasprogrammed to feed at a constant rate of 31.8 g/min. Anhydrouscyclohexane (2×200 ml) was charged to the styrene feed system to flushthe alumina bed. The styrene feed to the reactor was deemed completewhen no further heat of reaction was observed generally signified by theclosing of the automated control valve on the coiling coils.

The PID temperature controller was set at 80° C. and water was fedthrough the cooling coils while the flow of the hot oil was altered tobypass the reactor jacket. The reaction mixture was quenched at 80° C.with a 50 ml aliquot of deoxygenated water resulting in a water whiteturbid mixture. The reaction mixture was washed with deoxygenated water(3 times, 650 ml). Phase cuts were rapid and required little settlingtime. Water and any rag or emulsion was removed through the bottom drainvalve.

The temperature oil jacket was increased to 130° C. while the controlvalve to the cooling coils turned off. Cyclohexane, residual moistureand toluene were distilled through a simple distillation head (1 atm.)until a pot temperature of 115° C. was observed. An aliquot was removedfor analysis via GPC (M_(r): 397, M_(n): 652, M_(w): 1174, M_(z): 1853,PD: 1.80)

The crude reaction mixture, 8967 g, was stripped via continuousoperation of excess toluene to yield 2846 g of the concentrated productstream that had the following GPC analysis: M_(r): 295, M_(n): 674,M_(w): 1194, M_(z): 1877, PD: 1.77. The continuous strip wasaccomplished by means of wiped film evaporator (WFE, aka. Pope Still).WFE operating conditions were as follows: feed rate=1.33 L/hr, oiljacket temperature=160° C., Pressure=90 mm Hg and condensertemperature=0° C. Additionally 1024 g of toluene was collected in a dryice trap, while the cold finger condensed 5002 g of a mixture of tolueneand 1,3-diphenylpropane.

Examples 11 and 12 Continuous Mode Example 11 ACTSP-11 M_(w)=4054PD=2.14

The apparatus was a glass 200 mL oil jacketed baffled cylindricalreactor with an overflow port equipped with a nitrogen inlet, overheadstainless steel stirring shaft with pitched blade turbine impeller, anda thermal couple. The reactor was also outfitted with two subsurfacefeed lines: (1) a stainless steel ⅛″ (32 mm) O.D. line for introducing amixture of styrene and toluene; and (2) a stainless steel 1/16″ (16 mm)O.D. line for feeding a mixture formed from butyl lithium TMEDA andtoluene. The 1/16″ (16 mm) line was threaded through a ¼″ (6.4 mm) lineto prevent entanglement with the mechanical stirring apparatus duringthe course of a run. The tip of the 1/16 inch (16 mm) feed line wasdirected just below the impeller. The overflow port was directeddownward at a 22.5° angle, and was attached by means of a 13 mm AceThread® Teflon® connection to a 24-inch long glycol jacketed 15 mm O.D.glass tube. The other end of the 15 mm glass tube was connected to a 2liter, glycol jacketed stirred reactor by means of a second 13 mm AceThread® Teflon® connection (neither Teflon® couplings were wettedparts). The overflow reactor was equipped with an all-glass overheadstirring apparatus, bottom drain valve, chilled water condenser, andnitrogen oil-bubbler outlet. The overflow line and reactor were heatedto 100° C. with glycol.

In a stirred, oven-dried pear-shaped 500 ml flask under an inert N₂atmosphere at ambient temperature, an organolithium mixture was formedfrom 91.75 g (106 mL, 1.09 mol) of anhydrous toluene, 42.98 mL of 16.5wt % (5.28 g, 0.0824 mol contained alkyl lithium) n-butyl lithium incyclohexane and 8.62 g (11.19 mL, 0.0742 mole) TMEDA; this mixture wasstirred with a glass coated (no PTFE) magnetic stirring bar. About onehalf of the solution was drawn through a 1/16″ (16 mm) stainless steelthree-way ball valve into an oven dried 100 ml glass syringe mounted ona syringe pump. After infusion of the syringe, the ball valve was linedup such that the path from the syringe to the 1/16″ (16 mm) subsurfacefeed line in the reactor was open and the path to the magneticallystirred flask was closed. During the course of a reaction, the infusionof the syringe with the second half of the mixture was achieved bylining the 3-way ball valve such that the path to the flask was open andthe path to the reactor was closed.

At the start of the run, the reactor was charged with 100 mL ofanhydrous toluene and heated to 110° C. Meanwhile, 547 g (602 mL, 5.25mol) of styrene and 1734 g (2000 mL, 20.6 mol) of anhydrous toluene werecombined, mixed and then charged to a N₂-blanketed 3000 ml graduatedcylinder reservoir. The toluene-styrene mixture was pumped to thereactor with a laboratory-metering pump through a column of anhydrousbasic alumina until the first drop or two were seen entering thereactor; the feed was stopped and stirring in the reactor was initiated(˜400 rpm). Butyl lithium in cyclohexane was charged dropwise into thereactor by means of a 1.0 mL syringe. The addition was stopped when thecharacteristic red color of the polystyryllithium anion appeared(indicating anhydrous conditions). Next, about 4.8 g (0.012 mol) of 16.5wt % n-butyl lithium and 1.3 g (0.011 mol) of TMEDA were charged to thereactor. The feed rates of both feeds (toluene-styrene mixture andorganolithium mixture) were preset (toluene-styrene mixture: 6.28mL/min; organolithium mixture: 0.386 mL/min) and the pumps werecalibrated such that 200 ml of combined feed passed through the reactorper hour (two reactor volumes per hour) for a 30-minute residence time.The process was conducted for about 195 minutes at 110° C.

Samples were collected approximately every 30 minutes after the first45-minute period. It was found that within two reactor volumes, thesystem had reached steady state conditions. The GPC molecular weightdistribution of the first fraction collected was as follows: M_(w)=1992,M_(p)=2209, M_(n)=716 Daltons, M_(z)=3512 and Polydispersity=2.78. Atypical steady state fraction analyzed as follows: M_(w)=4146,M_(p)=4507, M_(n)=1656, M_(z)=7134 Daltons and Polydispersity=2.50. GPCanalysis of a composite of steady state fractions analyzed afterstripping toluene and 1-3-diphenylpropane was as follows: M_(w)=4051,M_(p)=3822, M_(n)=1879, M_(z)=6897 Daltons and Polydispersity=2.15

Example 12 ACTSP-12 M_(w)=2288 PD=1.91

The run in this Example repeats that of Example 11, except as describedherein. The toluene-styrene mixture was made from 547 g (602 mL, 5.25mol) of styrene and 1816 g (2100 mL, 21.58 mol) of anhydrous toluene.The organolithium mixture was formed from 177.27 g (2.11 mol, 205 mL) ofanhydrous toluene, 90.26 mL of 16.5 wt % (11.08 g, 0.173 mol containedalkyl lithium) n-butyl lithium in cyclohexane and 24.81 g (19.10 mL,0.1644 mole) TMEDA. After the red color of the polystyryllithium anionappeared, about 10 g (0.024 mol) of 16.5 wt % n-butyl lithium and 2.6 g(0.022 mol) of TMEDA were charged to the reactor. The feed rates of bothfeeds were preset (toluene-styrene mixture: 6.28 mL/min; organolithiummixture: 0.764 mL/min). The combined feed rate was one reactor volume(200 ml) per 28.4 minutes. The process was conducted for about 419minutes at 110° C.-113° C.

Samples were collected approximately every 30 minutes after the first 45minute period. It was found that within two reactor volumes, the systemhad reached steady state conditions. The GPC molecular weightdistribution of the first fraction collected was as follows: M_(w)=2154,M_(p)=2293, M_(n)=953, M_(z)=3510 Daltons and Polydispersity=1.65. Atypical steady state fraction analyzed as follows: M_(w)=2395,M_(p)=2410, M_(n)=1026, M_(z)=4246 Daltons and Polydispersity =2.34. GPCanalysis of a composite of steady state fractions analyzed afterstripping toluene and 1-3-diphenylpropane was as follows: M_(w)=2288,M_(p)=2094, M_(n)=1200, M_(z)=3767 Daltons and Polydispersity=1.91.

BROMINATION General Description:

Bromochloromethane (BCM) was azeotropically dried (5-10 ppm moisture byKarl Fisher). All feed lines, feed tanks and glassware were dried (ovendried at 130° C. min 2 hour where appropriate) and purged over-nightprior to use in the bromination reaction. All glassware, feed lines, andfeed tanks are maintained under a N₂ atmosphere during the course of theset-up and the operation of the bromination reactor.

The amount of AlBr₃ catalyst (commercially available) needed to make a0.25 mole % (calculated using the formula [moles AlBr₃/molesBr₂]*100%=0.25% mole % AlBr₃) solution of active catalyst was weighedand then transferred to oven dried reagent bottles in a nitrogen-purgedglove box. By active catalyst, it is meant that amount of catalyst aboveany additional amount that would be otherwise deactivated by moistureeither in the bromine itself or any other process stream involved in thebromination reaction. Bromine (5-10 ppm moisture content) was pumpedinto the reagent bottle containing the AlBr₃ and then stirred with aPTFE coated magnetic stirring bar for 30 minutes to assure homogenousdissolution of the catalyst. The 0.25 mole % AlBr₃ in bromine solutionwas then transferred to a graduated feeding vessel placed on a largecapacity laboratory balance.

The anionic chain-transfer styrene polymer (ACTSP) used was dissolved indry (5-10 ppm moisture) BCM to make a 25-wt % solution. The solution wasthen charged to a graduated feeding vessel. The 0.25 mole % AlBr₃ inbromine and the 25 wt % ACTSP in BCM solution are co-fed via separateperistaltic pumps through ⅛″ (32 mm) O.D. feed lines to a well-stirredfresh or recycle heel of anhydrous BCM at 0° C.-10° C. The relative feedrates are constantly monitored such that ratio of the two reagents fedremains constant or near constant during the course of the electrophilicbromination reaction.

Bromination Equipment Set-up:

A 5 L oil jacketed flask (bromination reactor) was equipped with an overhead glass stirrer shaft, PTFE stirring paddle, a water-cooledcondenser, thermo-well, nitrogen inlet, and bottom drain valve. Thereactor was vented through a calcium sulfate moisture trap to awell-stirred caustic scrubber to absorb co-product HBr and entrainedBr₂. Additionally the reactor was outfitted with three inlet lines: 1)¼″ (6.4) O.D. PTFE BCM feed for initial feed of BCM to the reactor (theBCM can be either fresh or a BCM recycle heel from a previous run); 2)⅛″ (32 mm) O.D. substrate/BCM subsurface feed line; and 3) ⅛″ (32 mm)O.D. Br₂/AlBr₃ subsurface feed line. The AlBr₃/Br₂ and ACTSP/BCM feedlines are secured such that both inlet lines discharge their contents inclose proximity creating a locally high reagent concentration. Thebromination reactor was completely covered with aluminum foil to excludelight and the reaction was conducted in a darkened ventilation hood.

The bromination reactor was placed above a 6-liter water quench pot witha ⅜″ (9.5 mm) O.D. PTFE drain line that connects the bottom drain valveof the bromination reactor to the quench pot to allow for directtransfer of the bromination reactor's contents. The quench pot was oiljacketed and equipped with an over-head stirring mechanism, thermowell,sodium bisulfite addition funnel and was baffled for intimate mixing oforganic and aqueous phases. The quench pot had a nitrogen inlet and waspurged to a caustic scrubber. The quench pot had a bottom drain valve toenable transfer of the pot's contents to an intermediate 5 liter storagevessel.

The intermediate storage vessel was piped to transfer its contents to awash kettle. The wash kettle was a 6-liter oil-jacketed, baffled reactoroutfitted with an over-head stirrer, reverse phase Dean Stark trap,thermocouple and bottom drain valve.

Alternative pieces of equipment are suitable for recovering thebrominated product as a solid and essentially free of BCM. Productrecovery can be effected by distilling off the BCM in an oil jacketedresin kettle to form a concentrate. The kettle is located to enable itsconcentrate product to in turn be dropped as a melt into a bucket ofwell-stirred (high shear) cold water. The stirring produces a granular(chopped) product (after oven drying) that is suitable for compoundinginto a formulation. The alternative set-up provides a water-containingvessel into which unconcentrated product is fed accompanied by theconcomitant azeotropic removal of BCM. The granules from the first andthe precipitate from the second, are passed through a vacuum oven fordrying Materials with glass transition temperature (T_(g)) below 100° C.are rinsed with methanol before drying in the oven at a temperature 15°C. below their T_(g).

A recapitulation of process parameters and analytical data on the finalcompositions contained for each of the Bromination Examples is found inTable I.

Bromination Example 1

To the 5 L bromination reactor described above was charged 867 g of dryBCM (azeotropically dried to 5-10 ppm moisture, Karl Fisher). The BCMwas cooled in the dark to −1° C. and a previously prepared 25 wt %solution comprised of 334 g of ACTSP-1 (From ACTSP Example 1 M_(w)=483,PD=1.32) and 1002 g of dry BCM was charged to a dry, 2000 ml N₂blanketed graduated cylinder outfitted with a ⅛″ (32 mm) PTFE feed lineplaced to transfer the entire content of the cylinder by means of aperistaltic metering pump to the bromination reactor. The previouslyprepared AlBr₃ (0.25 mol %) in bromine (1356 g) was transferred via aperistaltic pump into a 1.5 liter graduated cylinder. This feed vesselwas maintained under a N₂ atmosphere and was outfitted with a ⅛″ (32 mm)PTFE feed line placed to transfer the desired amount of bromine solutionby means of a peristaltic metering pump to the bromination reactor.

The two reagents are co-fed at predetermine relative rates such that theentire content of the two feeds are charged and simultaneously completedin 180 minutes. The co-feed was interrupted and the entire content ofthe reactor transferred to the quench pot on 60-minute intervalsresulting in a 30-minute average residence time for the reagents. A newheel was created in the bromination flask of 867 g of dry BCM each timeprior to resumption of the cofeed. Ample cooling was provided throughout the operation such that the reaction temperature remains close to−3° C. Upon completion of the feed the reaction was allowed to stir foran additional 5 minutes to allow unreacted bromine to be consumed. Thereaction mixture was transferred (gravity) to the 6 L quench pot throughthe bottom drain valve and the ⅜″ (9.5 mm) O.D. PTFE transfer line.

The quench pot was previously charged with 1000 ml tap water (25° C.)and stirred at 400 rpm to assure intimate mixing of the organic andaqueous phase. Upon completion of the transfer, 10% Na₂SO₃ solution wasadded until the red color was eliminated and a near water white mixturewas observed. The quench was exothermic and a 10° C. temperature risewas observed. Agitation was stopped and the organic phase allowed tosettle. The lower organic phase was transferred to a 5 L storage vesselcontaining 1000 ml of 10% NaOH and 1.0 g NaBH₄.

This two-phase system was then transferred to the 6 L wash kettle andrefluxed (62° C.) for 30 minutes. Agitation was interrupted and thebottom organic layer cut from the reactor. The organic layer wasreturned to the completely drained kettle and washed twice with 1000 mlof tap water to a pH of 10. The solution was then azeotropically driedby means of a reverse phase Dean-Stark trap. The content of the reactorwas pumped to a 1 liter resin kettle while stripping BCM at atmosphericpressure. Upon completion of the transfer, the BCM strip was continuedat atmospheric pressure until the pot temperature reached 150° C. BCMwas then further removed in vacuo to an ending condition of 150° C. and<5 mm Hg.

The content of the resin kettle was drained into a 2.5-gallon plasticpail of rapidly stirred (high sheer blade, 2100 rpm) cold water to grindthe product into a coarse powder. The product was collected in a 3000 mlcoarse fitted Büchner funnel, rinsed with methanol and then dried in avacuum oven (25° C.) to yield 955 g of the brominated product.

Bromination Example 2

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-1 (From ACTSP Example 1 Mw=483, PD=1.32) indry BCM was co-fed with 257 g of 0.25 mole % AlBr3 in bromine to a heelof 3850 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at45° C. in a vacuum oven. The procedure produced 1688 g of product.

Bromination Example 3

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-1 (From ACTSP Example 1 M_(w)=483, PD=1.32) indry BCM was co-fed with 2846 g of 0.25 mole % AlBr₃ in bromine to a heelof 3850 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at65° C. in a vacuum oven. The procedure produced 1823 g of product.

Bromination Example 4

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-2 (From ACTSP Example 2 M_(w)=496, PD=1.32) indry BCM was co-fed with 2895 g of 0.25 mole % AlBr₃ in bromine to a heelof 3500 g of BCM at a constant uninterrupted relative feed rate so thatthe average residence time in the reactor was 90 minutes. The crudeproduct mixture was heterogeneous and required the addition of 0.125 gof sodium dodecyl sulfate to each aqueous wash to break the resultingemulsions and achieve the desired phase cut. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 130° C. in a vacuum oven. The procedure produced1645 g of product.

Bromination Example 5

The procedure of Bromination Example 1 was used except that 1165 g of a25 wt % solution of ACTSP-2 (From ACTSP Example 2 M_(w)=496, PD=1.32) indry BCM was co-fed with 2330 g of 0.25 mole % AlBr₃ in bromine to a heelof 3200 g of BCM at a constant uninterrupted relative feed rate so thatthe average residence time in the reactor during the feed was 90minutes. The reaction mixture was allowed to stir for an additional 60minutes after completion of the co-feed. The crude product mixture washeterogeneous and required the addition of 0.125 grams of sodium dodecylsulfate to each aqueous wash to break the resulting emulsions andachieve the desired phase cut. The washed product mixture was filteredand the resulting filter cake washed with BCM and dried in a vacuum ovenat 150° C. to yield 557 g of a white solid. The filtrate and wash BCMwere combined and the soluble portion of the product precipitated fromwater at 95° C. with concomitant stripping of BCM. The BCM-solubleproduct fraction was dried at 130° C. in a vacuum oven to yield 693 g ofa white solid.

Bromination Example 6

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-3 (From ACTSP Example 3 M_(w)=530, PD=1.47) indry BCM was co-fed with 2846 g of 0.25 mole % AlBr₃ in bromine to a heelof 4000 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at65° C. in a vacuum oven. The procedure produced 1730 g of product.

Bromination Example 7

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-3 (From ACTSP Example 3 M_(w)=530, PD=1.47) indry BCM was co-fed with 2704 g of 0.25 mole % AlBr₃ in bromine to a heelof 4000 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at45° C. in a vacuum oven. The procedure produced 1751 g of product.

Bromination Example 8

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-3 (From ACTSP Example 3 M_(w)=530, PD=1.47) indry BCM was co-fed with 2846 g of 0.25 mole % AlBr₃ in bromine to a heelof 4200 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at45° C. in a vacuum oven. The procedure produced 1853 g of product.

Bromination Example 9

The procedure of Bromination Example 1 was used except that 1336 g of a25 wt % solution of ACTSP-4 (From ACTSP Example 4 M_(w)=584, PD=1.50) indry BCM was co-fed with 1356 g of 0.25 mole % AlBr₃ in bromine to a heelof 2600 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at30° C. in a vacuum oven. The procedure produced 933 g of product.

Bromination Example 10

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-4 (From ACTSP Example 4 M_(w)=584, PD=1.50) indry BCM was co-fed with 2333 g of 0.25 mole % AlBr₃ in bromine to a heelof 4000 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at35° C. in a vacuum oven. The procedure produced 1540 g of product.

Bromination Example 11

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-4 (From ACTSP Example 4 M_(w)=584, PD=1.50) indry BCM was co-fed with 2846 g of 0.25 mole % AlBr₃ in bromine to a heelof 4200 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at60° C. in a vacuum oven. The procedure produced 1677 g of product.

Bromination Example 12

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-4 (From ACTSP Example 4 M_(w)=584, PD=1.50) indry BCM was co-fed with 3167 g of 0.25 mole % AlBr₃ in bromine to a heelof 3850 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at65° C. in a vacuum oven. The procedure produced 1640 g of product.

Bromination Example 13

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-5 (From ACTSP Example 5 M_(w)=715, PD=1.40) indry BCM was co-fed with 2125 g of 0.25 mole % AlBr₃ in bromine to a heelof 3800 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at60° C. in a vacuum oven. The procedure produced 1462 g of product.

Bromination Example 14

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-5 (From ACTSP Example 5 M_(w)=715, PD=1.40) indry BCM was co-fed with 2571 g of 0.25 mole % AlBr₃ in bromine to a heelof 4000 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product was dried at70° C. in a vacuum oven. The procedure produced 1601 g of product.

Bromination Example 15

The procedure of Bromination Example 1 was used except that 1600 g of a25 wt % solution of ACTSP-5 (From ACTSP Example 5 M_(w)=715, PD=1.40) indry BCM was co-fed with 2276 g of 0.25 mole % AlBr₃ in bromine to a heelof 3500 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 90° C. in a vacuum oven. The procedure produced1427 g of product.

Bromination Example 16

The procedure of Bromination Example 1 was used except that 2000 g of a25 wt % solution of ACTSP-6 (From ACTSP Example 6 M_(w)=740, PD=1.66) indry BCM was co-fed with 2846 g of 0.25 mole % AlBr₃ in bromine to a heelof 4200 g of BCM at a constant relative feed rate so that the averageresidence time in the reactor was 30 minutes. The product wasprecipitated from water at 92° C. with concomitant stripping of BCM. Theproduct was dried at 90° C. in a vacuum oven. The procedure produced1820 g of product.

Bromination Example 17

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-7 (From ACTSP Example 7 M_(w)=800, PD=1.39) indry BCM was co-fed with 1836 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 90° C. in a vacuum oven. The procedureproduced 1250 g of product.

Bromination Example 18

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-7 (From ACTSP Example 7 M_(w)=800, PD=1.39) indry BCM was co-fed with 2135 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 110° C. in a vacuum oven. The procedureproduced 1400 g of product.

Bromination Example 19

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-7 (From ACTSP Example 7 M_(w)=800, PD=1.39) indry BCM was co-fed with 2135 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the co-feed was completed in 180 minutes. Upon completion of thefeed the reaction mixture was warmed to 25° C. over a 1 hr period, thusproviding an average residence time in excess of 120 minutes. Theproduct mixture was transferred to the quench pot and no sulfite wasadded to treat unreacted bromine. Unreacted bromine was converted tobromide during the caustic NaBH₄ wash. The product was precipitated fromwater at 95° C. with concomitant stripping of BCM. The product was driedat 110° C. in a vacuum oven. The procedure produced 1401 g of product.

Bromination Example 20

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-7 (From ACTSP Example 7 M_(w)=800, PD=1.39) indry BCM was co-fed with 2375 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the co-feed was completed in 180 minutes. Upon completion of thefeed the reaction mixture was warmed to 25° C. over a 1 hr period, thusproviding an average residence time in excess of 120 minutes. The crudeproduct mixture was heterogeneous and required the addition of 0.125grams of sodium dodecyl sulfate to each aqueous wash to break theresulting emulsions and achieve the desired phase cut. The productmixture was transferred to the quench pot and no sulfite was added totreat unreacted bromine. Unreacted bromine was converted to bromideduring the caustic NaBH₄ wash. The product was precipitated from waterat 95° C. with concomitant stripping of BCM. The product was dried at110° C. in a vacuum oven. The procedure produced 1460 g of product.

Bromination Example 21

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-8 (From ACTSP Example 8 M_(w)=817, PD=1.26) indry BCM was co-fed with 1836 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 100° C. in a vacuum oven. The procedureproduced 1230 g of product.

Bromination Example 22

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-8 (From ACTSP Example 8 M_(w)=817, PD=1.26) indry BCM was co-fed with 2135 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 110° C. in a vacuum oven. The procedureproduced 1320 g of product.

Bromination Example 23

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-8 (From ACTSP Example 8 M_(w)=817, PD=1.26) indry BCM was co-fed with 2659 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. The crudeproduct mixture was heterogeneous and required the addition of 0.125grams of sodium dodecylsulfate to each aqueous wash to break theresulting emulsions and achieve the desired phase cut. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 130° C. in a vacuum oven. The procedure produced1440 g of product.

Bromination Example 24

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-9 (From ACTSP Example 9 M_(w)=928, PD=1.43) indry BCM was co-fed with 1836 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 100° C. in a vacuum oven. The procedureproduced 1250 g of product.

Bromination Example 25

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-9 (From ACTSP Example 9 M_(w)=928, PD=1.43) indry BCM was co-fed with 2135 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. Theproduct was precipitated from water at 95° C. with concomitant strippingof BCM. The product was dried at 110° C. in a vacuum oven. The procedureproduced 1388 g of product.

Bromination Example 26

The procedure of Bromination Example 1 was used except that 1500 g of a25 wt % solution of ACTSP-9 (From ACTSP Example 9 M_(w)=928, PD=1.43) indry BCM was co-fed with 2659 g of 0.25 mole % AlBr₃ in bromine to a heelof 3000 g of BCM at a constant and uninterrupted relative feed rate sothat the average residence time in the reactor was 90 minutes. The crudeproduct mixture was heterogeneous and required the addition of 0.125grams of sodium dodecylsulfate to each aqueous wash to break theresulting emulsions and achieve the desired phase cut. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 130° C. in a vacuum oven. The procedure produced150 g of product.

Bromination Example 27

The procedure of Bromination Example 1 was used except that 1400 g of a25 wt % solution of ACTSP-10 (From ACTSP Example 9 M_(w)=1194, PD=1.77)in dry BCM was co-fed with 1800 g of 0.25 mole % AlBr₃ in bromine to aheel of 3200 g of BCM at a constant relative feed rate so that theaverage residence time in the reactor was 30 minutes. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 105° C. in a vacuum oven. The procedure produced 89g of product.

Bromination Example 28

The procedure of Bromination Example 1 was used except that 1400 g of a25 wt % solution of ACTSP-10 (From ACTSP Example 9 M_(w)=1194, PD=1.77)in dry BCM was co-fed with 2045 g of 0.25 mole % AlBr₃ in bromine to aheel of 4000 g of BCM at a constant relative feed rate so that theaverage residence time in the reactor was 30 minutes. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 120° C. in a vacuum oven. The procedure produced1245 g of product.

Bromination Example 29

The procedure of Bromination Example 1 was used except that 1392 g of a25 wt % solution of ACTSP-11 (From ACTSP Example 11 M_(w)=4051, PD=2.15)in dry BCM was co-fed with 1479 g of 0.25 mole % AlBr₃ in bromine to aheel of 3000 g of BCM at a constant relative feed rate so that theaverage residence time in the reactor was 30 minutes. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 130° C. in a vacuum oven. The procedure produced980 g of product.

Bromination Example 30

The procedure of Bromination Example 1 was used except that 1360 g of a25 wt % solution of ACTSP-12 (From ACTSP Example 12 M_(w)=2288, PD=1.91) in dry BCM was co-fed with 1445 g of 0.25 mole % AlBr₃ in bromineto a heel of 3200 g of BCM at a constant relative feed rate so that theaverage residence time in the reactor was 30 minutes. The product wasprecipitated from water at 95° C. with concomitant stripping of BCM. Theproduct was dried at 115° C. in a vacuum oven. The procedure produced1002 g of product.

TABLE I Bromination example 1 2 3 4 5 6 7 8 9 10 ACTSP Example 1 1 1 2 23 3 3 4 4 ACTSP M_(w) 483 483 483 496 496 530 530 530 584 584 ACTSP PD1.32 1.32 1.32 1.32 1.32 1.47 1.47 1.47 1.50 1.50 ACTSP (g) 334 500 500375 291.3 500 500 500 334 500 Moisture (ppm) 58 66 66 5 5 26 26 26 14 11ppm Wt % in BCM 25 25 25 25 25 25 25 25 25 25 BCM in Feed (g) 1002 15001500 1125 873.9 1500 1500 1500 1002 1500 Bromine (g) 1356.24 2571.432846.15 2895.3 2330.4 2846.15 2703.7 2846.15 1356.24 2333.3 BCM inReactor 2600 3850 4200 3500 3200 4000 4000 4200 2600 4000 (g) Rxn Temp−3 −2 −2 −5 −3 (−6~−1.1) −5 −4 −4 (−6~−2) −3 (−4~−2) −4 (−6~−1) (range °C.) (−4~−2) (−4~−1) (−4~−1) (−6~−2) (−6~−3.5) (−5.3~−3) Average 30 30 3090 >120 30 30 30 30 30 residence time(min) Solids from ML 103 0 0 0 5570 50.3 0 0 0 180.5 (g) part part a b Mass of Product 954.9 1688.111823.53 1550 557 693 1730.2 1751.9 1853.2 933.05 1540.75 TheoreticalYield 1012 1806 1923 1645 (a + b) 1306 1819 1880 1976 1044 1678 % Yield105% 93% 95% 94% 96% 98% 93% 94% 89% 103% Bromination example ProductAnalyses 1 2 3 4 5a 5b 6 7 8 9 10 Residual BCM (ppm) 270 430 220 9602830 90 240 17600 3750 310 XRF wt % Br 68.3 73.2 74.3 78.4 N/A 78.7 75.172.5 74.7 68.5 71.1 bromine per ring 2.7 3.5 3.7 4.6 4.7 3.8 3.4 3.7 2.83.1 Tg (° C.) (DSC) 37.7 57.4 74.66 139 222 140.86 72.3 60.76 52.4438.06 43.23 TGA (N₂)  1% Wt. Loss (° C.) 230 259 273 322 320 331 268 258154 169 212  5% Wt. Loss (° C.) 290 308 327 365 362 367 318 311 300 283292 10% Wt. Loss 317 334 354 380 375 380 342 337 335 314 323 (° C.) 50%Wt. Loss 390 391 395 418 415 412 395 398 394 398 384 (° C.) Thermal HBr73 349 248 314 208 363 463 333 315 131 <50 300° C. (ppm) GPC Mw 15522092 2180 3041 N/A 3066 1561 2359 2410 2014 2250 Mn 958 1819 1880 2605N/A 2596 1391 2013 1700 1560 2040 Mz 2060 2549 2787 3713 N/A 3792 19222945 4250 2677 2585 PD 1.6 1.15 1.16 1.17 N/A 1.18 1.12 1.17 1.4 1.291.1 Color (YI Powder) 2.82 3.66 6.88 Color (solution) L 100.36 98.9898.55 98.69 N/A 97.4 99.08 97.32 96.98 96.79 96.2 a 0.01 −0.06 −0.1−0.65 N/A −1.52 −0.47 −0.19 −0.32 −0.96 −0.9 b 0.74 2.47 3.33 4.9 N/A9.97 6.5 6.07 7.79 5.7 8.08 ΔE 0.82 2.67 3.63 5.11 N/A 10.41 6.58 6.648.36 6.61 8.97 Bromination example 11 12 13 14 15 16 17 18 19 20 ACTSPExample 4 4 5 5 5 6 7 7 7 7 ACTSP M_(w) 584 584 715 715 715 740 800 800800 800 ACTSP PD 1.50 1.50 1.40 1.40 1.40 1.66 1.39 1.39 1.39 1.39 ACTSP(g) 500 500 500 500 400 500 375 375 375 375 Moisture (ppm) 11 11 9 9 911 19 19 19 19 Wt % in BCM 25 25 25 25 25 25 25 25 25 25 BCM in Feed (g)1500 1500 1500 1500 1200 1500 1125 1125 1125 1125 Bromine (g) 2846.153166.67 2125 2571.43 2276 2846.15 1836.2 2134.6 2134.6 2375 BCM inReactor 4200 3850 3800 4000 3500 4200 3000 3000 3000 3000 (g) Rxn Temp−4 −2 −5.5 (−7~−3) −5 −3 (−4~−1) −4 (−6~−2) −4 (−5~−2) −4 (−5~−2) −4(−5~−2) −4 (−5~−2) (range ° C.) (−6~−1) (−4~−1) (−6~−3) Average 30 30 3030 30 30 90 90 >120 >120 residence time(min) Solids from ML 33.37 113.040 0 0 0 0 0 0 (g) Mass of Product 1677.7 1641.0 1462.9 1601.5 1426.81820.0 1250.0 1400.1 1401.0 1460 Theoretical Yield 1880 1986 1582 17361556 2000 1307 1448 1465 1563 % Yield 91% 88% 92% 92% 92% 91% 96% 97%96% 93% Product Analyses Residual BCM 270 190 250 220 7520 1200 29 0 84<30 (ppm) XRF wt % Br 74.1 75.5 68.4 71.7 74.2 76.2 72.3 74.7 75.2 76.5bromine per ring 3.6 3.9 2.8 3.2 3.7 4.1 3.3 3.8 3.9 4.2 Tg (° C.) (DSC)73.11 93.11 75.33 87.94 111.1 102.02 104.6 131.7 136.9 158.1 TGA (N₂) 1% Wt. Loss 236 265 316 314 210 273 273 339 341 347 (° C.)  5% Wt. Loss306 334 351 348 351 339 320 366 370 375 (° C.) 10% Wt. Loss 335 357 363361 365 360 339 378 380 386 (° C.) 50% Wt. Loss 388 401 393 393 401 406382 411 410 416 (° C.) Thermal HBr 357 199 251 <50 254 160 347 163 158<50 300° C. (ppm) GPC Mw 2100 2990 2630 2840 3109 4000 3050 3280 35103599 Mn 1200 2440 2170 2180 2665 3160 2530 2720 2663 2780 Mz 3713 39633460 3918 3815 5460 3720 4020 4815 4871 PD 1.75 1.23 1.21 1.30 1.17 1.301.20 1.21 1.32 1.29 Color 3.98 (YI Powder) Color (solution) L 98.3498.48 95.02 95.18 100.3 99.58 100.05 100.95 99.5 98.61 a −1.95 −1.94−1.79 −1.49 −2.59 −0.18 0.05 −0.11 −0.36 −0.76 b 8.77 11.48 14.58 15.677.56 1.45 0.46 0.51 2.18 4.76 ΔE 9.14 11.74 15.51 16.46 8.00 1.52 0.471.08 2.27 5.02 Bromination example 21 22 23 24 25 26 27 28 29 30 ACTSPExample 8 8 8 9 9 9 10 10 11 12 ACTSP M_(w) 817 817 817 928 928 928 11941194 4054 2288 ACTSP PD 1.27 1.27 1.27 1.43 1.43 1.43 1.77 1.77 2.151.91 ACTSP (g) 375 375 375 375 375 375 350 350 348 340 Moisture (ppm) 8989 89 12 12 12 12 12 145 94 Wt % in BCM 25 25 25 25 25 25 25 25 25 25BCM in Feed (g) 1125 1125 1125 1125 1125 1125 1050 1050 1044 1020Bromine (g) 1836 2135 2659 1836 2135 2659 1800 2045 1479 1445 BCM inReactor 3000 3000 3000 3000 3000 3500 3200 4000 3200 3000 (g) Rxn Temp−4 −4 −4 −5 −5 −4.7 −3.8 (−4~−2) −3.8 (−4~−2) −3.8 (−5~−3) −3.8 (−4~−2)(range ° C.) (−6~−2.5) (−6~−2.5) (−6~−2.5) (−6~−2) (−6~−2) (−6~2)Average 90 90 90 90 90 90 30 30 30 30 residence time(min) Solids from ML0 0 0 0 0 0 0 0 0 0 (g) Mass of Product 1230 1320 1440 1250 1388 1500891 1244.53 980.5 1002.25 Theoretical Yield 1339 1442 1563 1339 15001563 1296 1346 1094 1063 % Yield 92% 92% 92% 93% 93% 96% 69% 92% 90% 94%Product Analyses Residual BCM <50 30 70 0 0 90 <50 160 1550 320 (ppm)XRF wt % Br 72.5 74.4 76.4 72.7 73.5 77.5 73.1 74.6 68.6 68.6 bromineper ring 3.4 3.7 4.1 3.4 3.6 4.4 3.5 3.7 2.8 2.8 Tg (° C.) (DSC) 112.3137.2 163.02 112.6 142.5 163.1 117.44 140.35 150.34 133.79 TGA (N₂)  1%Wt. Loss 328 340 359 321 336 350 295 320 320 332 (° C.)  5% Wt. Loss 358370 383 353 367 373 343 359 359 360 (° C.) 10% Wt. Loss 370 380 391 366378 383 361 373 371 370 (° C.) 50% Wt. Loss 403 412 419 399 413 413 400408 401 402 (° C.) Thermal HBr 309 127 82 226 <50 256 265 269 72 <50300° C. (ppm) GPC Mw 3740 3700 3400 3689 4093 4232 4080 4070 14000 7900Mn 3100 2990 2710 2778 3104 3107 1970 1800 8100 3800 Mz 4810 4780 40305135 5737 6206 6831 7049 20642 12131 PD 1.2 1.24 1.25 1.33 1.32 1.3622.07 2.26 1.74 2.08 Color 5.71 (YI Powder) Color (solution) L 100.2999.27 98.82 99.29 99.6 N/A 99.15 99.34 98.58 98.1 a −0.28 −0.42 −0.65−0.23 −0.54 N/A −2.15 −2.08 −1.07 −1.88 b 1.83 2.87 3.64 2.95 2.81 N/A6.47 6.06 5.2 7.69 ΔE 1.87 2.99 3.88 3.04 2.89 N/A 6.87 6.44 5.50 8.14

HIPS and ABS Formulations

General Procedure for Compounding, Injection Molding and Testing of HIPSand ABS Formulated with CLASP Materials.

HIPS

The HIPS resin and the flame-retardant in addition to antimony oxidewere mixed in a plastic bag using a tumble mixer for approximately 10minutes prior to extrusion. The compounding was conducted on a Werner &Pfleiderer ZSK30 twin-screw extruder at 175 rpm. The feed rate was 8kg/hr. The temperature profile was 175-175-190-215-215° C. In somecases, the first zone temperature was lowered to 125-150° C. in order toavoid sticking issues at feed throat. A trap was used to capture anyvolatiles if there was any. The extruded strand was first cooled down bypassing an iced-water bath and then pelletized on-line. All formulationswere injection molded at a Battenfeld BA350 CD injection-moldingmachine. The temperature profile was 195-195-205° C. for most of thesamples. A lower feed zone temperature of 190° C. was used in somecases. The mold temperature was 40° C.

ABS

The ABS resin, flame-retardant, antimony oxide and antioxidant weremixed in a plastic bag using a tumble mixer for approximately 10 minutesprior to extrusion. The compounding was conducted on a Werner &Pfleiderer ZSK30 twin-screw extruder at 175 rpm. The feed rate was 8kg/hr. The temperature profile was 190-210-210-220-220° C. In somecases, the first zone temperature was lowered to 125-150° C. in order toavoid sticking issues at feed throat. A trap was used to capture anyvolatiles if there was any. The extruded strand was first cooled down bypassing an iced-water bath and then pelletized on-line. All formulationswere injection molded at a Battenfeld BA350 CD injection-moldingmachine. The temperature profile was 204-216-221° C. The moldtemperature was 40° C.

Testing was performed on HIPS and ABS samples according to the followingASTM test standards: VICAT (ASTM D649); Heat Deflection Temperatureunder Load (ASTM D648) ⅛″ (32 mm) at 264 psi; Notched-Izod ImpactStrength (ASTM D256 method A); and Melt Flow Index (ASTM D1238 procedureA), 200° C./5 kg. The UL-94 flammability test was performed on ⅛″ (32mm) bars. The results are reported in Table II.

Bromination 1 2 3 4 5 7 8 Example Dow 801 wt. % 81.1 82.2 82.5 83.2 83.382.3 82.5 (HIPS) Brightsun HB wt. % 4.0 4.0 4 4 4 4 4 (ATO) Br-FRLoading wt. % 14.9 13.8 13.5 12.8 12.7 13.7 13.5 PROPERTIES HDT, 264 psiASTM ° C. 68.4 70.8 69.3 73.0 73.0 68.4 69.3 D648 Vicat ASTM ° C. 96.1100 99.9 94.7 95.8 D649 Izod Impact ASTM ft-lb/in 1.44 1.34 1.36 1.481.51 1.34 1.36 D256 UL-94, ⅛″ UL-94 rating fail V-0 V-0 V-0 V-0 V-0 V-0(time) MFI, 200° C./ ASTM g/10 17.1 18.2 14.3 11.3 10.9 15.2 14.5 5 kgD1238 min

Bromination 10 11 12 13 14 15 Example Dow 801 wt. % 81.9 82.5 82.6 81.482.0 82.5 (HIPS) Brightsun HB wt. % 4.0 4.0 4.0 4.0 4.0 4 (ATO) Br-FRLoading wt. % 14.1 13.5 13.4 14.6 14.0 13.5 PROPERTIES HDT, 264 psi ASTM° C. 70.6 73.2 73.4 72.3 73.4 71.9 D648 Vicat ASTM ° C. 93.9 96.4 97.496.6 98 99.4 D649 Izod Impact ASTM ft-lb/in 1.36 1.42 1.42 1.30 1.331.33 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 V-0 V-0 MFI, 200° C./ASTM g/10 15.53 13.5 12.61 14.53 13.28 11.6 5 kg D1238 min

Bromination 16 17 18 19 21 22 23 Example Dow 801 wt. % 82.5 82.0 82.582.6 82.1 82.5 82.8 (HIPS) Brightsun HB wt. % 4 4 4 4 4 4 4 (ATO) Br-FRLoading wt. % 13.5 14.0 13.5 13.4 13.9 13.5 13.2 PROPERTIES HDT, 264 psiASTM ° C. 73.1 72.2 72.4 72.9 72.5 73.5 74.1 D648 Vicat ASTM ° C. 99.4100.7 100.8 99.9 101 101.2 D649 Izod Impact ASTM ft-lb/in 1.36 1.37 1.421.42 1.44 1.46 1.51 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 V-1 V-0V-0 MFI, 200° C./ ASTM g/10 12.7 12.1 10.3 10.1 11.5 10.4 9.1 5 kg D1238min

Bromination 24 25 26 27 28 29 30 Example Dow 801 wt. % 82.0 82.5 82.882.3 82.6 81.4 81.4 (HIPS) Brightsun HB wt. % 4 4 4 4 4 4 4 (ATO) Br-FRLoading wt. % 14.0 13.5 13.2 13.7 13.4 14.6 14.6 PROPERTIES HDT, 264 psiASTM ° C. 72.9 73.4 74.5 73.2 74 74.8 73.5 D648 Vicat ASTM ° C. 99.8100.9 101.2 D649 Izod Impact ASTM ft-lb/in 1.31 1.39 1.46 1.27 1.38 0.920.86 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 Fail* V-0 V-0 MFI, 200°C./ ASTM g/10 11.9 10.1 9.0 11.3 10.1 8.8 11 5 kg D1238 min

Bromination 3 4 5 6 7 10 11 Example Dow 342 EZ wt. % 79.2 80.0 80.1 79.478.8 78.3 79.1 Brightsun HB wt. % 4.5 4.5 4.5 4.5 4.5 4.5 4.5 (ATO)AT-181 wt. % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Br-FR Loading wt. % 16.2 15.415.3 16.0 16.6 17.1 16.3 PROPERTIES HDT, 264 psi ASTM ° C. 72.4 73.974.2 72.6 71.2 71.7 73.5 D648 Vicat ASTM ° C. 99.8 103.2 103 100.4 98.9D649 Izod Impact ASTM ft-lb/in 1.76 1.80 1.86 1.87 1.78 1.77 1.88 D256UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 MFI, 230° C./ ASTMg/10 11.6 10.1 10.2 11.0 11.8 11.9 11.2 3.8 kg D1238 min

Bromination 12 13 14 15 Example Dow 342 EZ wt. % 79.4 77.9 78.5 79.2Brightsun HB wt. % 4.5 4.5 4.5 4.5 (ATO) AT-181 wt. % 0.1 0.1 0.1 0.1Br-FR Loading wt. % 16.0 17.5 16.9 16.2 PROPERTIES HDT, 264 psi ASTM °C. 74.4 73.9 74.4 73.4 D648 Vicat ASTM ° C. 102.2 D649 Izod Impact ASTMft-lb/in 1.88 1.64 1.77 1.76 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0MFI, 230° C./ ASTM g/10 10.0 11.7 11.9 10.0 3.8 kg D1238 min

Bromination 16 17 18 19 21 22 23 Example Dow 342 EZ wt. % 79.4 78.6 79.279.3 78.7 79.2 79.6 Brightsun HB wt. % 4.5 4.5 4.5 4.5 4.5 4.5 4.5 (ATO)AT-181 wt. % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Br-FR Loading wt. % 16.0 16.816.2 16.1 16.7 16.2 15.8 PROPERTIES HDT, 264 psi ASTM ° C. 73.9 74 74.875.8 73.9 75.4 76.8 D648 Vicat ASTM ° C. 101.9 102.3 103.6 103.7 102.2103.4 103.9 D649 Izod Impact ASTM ft-lb/in 1.73 1.71 1.75 1.78 1.67 1.711.70 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 MFI, 230°C./ ASTM g/10 10.3 11.3 10.7 10.0 11.5 10.3 10.3 3.8 kg D1238 min

Bromination 24 25 26 27 28 Example Dow 342 EZ wt. % 78.6 79.2 79.6 79.079.3 Brightsun HB wt. % 4.5 4.5 4.5 4.5 4.5 (ATO) AT-181 wt. % 0.1 0.10.1 0.1 0.1 Br-FR Loading wt. % 16.8 16.2 15.8 16.4 16.1 PROPERTIES HDT,264 psi ASTM ° C. 74.4 76 76.1 74.8 75.2 D648 Vicat ASTM ° C. 102.9103.8 104.1 102.7 103.2 D649 Izod Impact ASTM ft-lb/in 1.58 1.63 1.681.66 1.76 D256 UL-94, ⅛″ UL-94 rating V-0 V-0 V-0 V-0 V-0 MFI, 230° C./ASTM g/10 10.6 10.1 9.1 10.5 10.2 3.8 kg D1238 min *fail due to afterglow

indicates data missing or illegible when filed

1. A flame retardant composition comprising a brominated anionic, chaintransfer, vinyl aromatic polymer (ACTVAP), wherein the composition: (i)contains at least about 72 wt % bromine; and (ii) contains less thanabout 1,000 ppm (weight/weight) thermally labile Br, the wt % and ppmvalues being based upon the total weight of the composition.
 2. Thecomposition of claim 1 wherein the composition has a TGA 5 wt % loss ata temperature of from about 280° C. to about 380° C. under nitrogen. 3.The composition of claim 1 wherein the brominated ACTVAP comprises atleast about 97 wt % of the total composition weight.
 4. The compositionof claim 1 wherein the composition contains less than 25 wt % brominatedmonoadduct, based on the total weight of the composition.
 5. Thecomposition of claim 1 wherein the composition has a Yellowness Index(ASTM D1925) within the range of from about 1 to about
 8. 6. Thecomposition of claim 1 wherein the composition obtains, via GPC, anM_(w) of from about 1250 to about 14,000 Daltons, and an M_(n) fromabout 1070 to about 8,200 Daltons and a PD less than about 2.2.
 7. Thecomposition of claims 1 wherein the brominated ACTVAP is brominatedanionic, chain transfer, styrene polymer (ACTSP).
 8. The composition ofclaim 7 wherein the composition has a TGA wt % loss of 5% at atemperature of from about 290 to about 380° C.
 9. The composition ofclaim 7 wherein the brominated ACTSP comprises at least about 97 wt % ofthe total composition weight.
 10. The composition of claim 7 wherein thecomposition has a Yellowness Index (ASTM D1925) of from about 1 to about8.
 11. The composition of claim 7 wherein the composition obtains, viaGPC, an M_(w) of from about 1250 to about 14,000 Daltons, and an M_(n)from about 1,070 to about 8,200 Daltons and a PD less than about 2.2.12. A HIPS-based formulation containing a flame retardant amount of thecomposition of claims 1 or
 7. 13. An ABS-based formulation containing aflame retardant amount of the composition of claims 1 or
 7. 14. Theformulation of claim 12 wherein the formulation additionally contains asynergistic amount of a flame retardant synergist.
 15. The formulationof claim 13 wherein the formulation additionally contains a synergisticamount of a flame retardant synergist.
 16. A flame retardant compositioncomprising a brominated anionic, chain transfer, vinyl aromatic polymer(ACTVAP), wherein the composition: (i) has a glass transitiontemperature (T_(g))) within the range of from about 35° C. to about 165°C.; (ii) contains at least about 65 wt % bromine; and (iii) containsless than about 1,000 ppm (weight/weight) thermally labile Br, the wt %and ppm values being based upon the total weight of the composition. 17.The composition of claim 16 wherein the composition has a glasstransition temperature (T_(g)) within the range of from about 75° C. toabout 135° C.
 18. The composition of claim 16 wherein the compositionhas a TGA 5 wt % loss at a temperature of from about 290° C. to about380° C.
 19. The composition of claim 16 wherein the brominated ACTVAPcomprises at least about 97 wt % of the total composition weight. 20.The composition of claim 16 wherein the composition contains less thanabout 25 wt % brominated monoadduct, based n the total weight of thecomposition.
 21. The composition of claim 16 wherein the composition hasa Yellowness Index (ASTM D1925) within the range of from about 1 toabout
 8. 22. The composition of claim 16 wherein the compositionsobtains, via GPC, an M_(w) of from about 1,000 to about 21,000 Daltons,and an M_(n) from about 850 to about 18,500 and a PD less than about2.2.
 23. The composition of claims 16 wherein the brominated ACTVAP isbrominated anionic, chain transfer, styrene polymer (ACTSP).
 24. Thecomposition of claim 23 wherein the composition has a glass transitiontemperature within the range of from about 70° C. to about 160° C. 25.The composition of claim 23 wherein the composition has a TGA wt % lossof 5% at a temperature of from about 290° C. to about 380° C.
 26. Thecomposition of claim 23 wherein the brominated ACTSP comprises at leastabout 97 wt % of the total composition weight.
 27. The composition ofclaim 23 wherein the composition has a Yellowness Index (ASTM D1925) offrom about 1 to about
 8. 28. The composition of claim 23 wherein thecomposition obtains, via GPC, an M_(w) of from about 1,000 to about21,000 Daltons, and an M_(n) from about 850 to about 18,500 and a PDthat is less than about 2.2.
 29. A HIPS-based formulation containing aflame retardant amount of the composition of claims 16 or
 23. 30. AnABS-based formulation containing a flame retardant amount of thecomposition of claim 16 or
 23. 31. A thermoplastic article containingany one or more of the compositions of claims 1, 7, 16 or 23.